Abstract
In this study, a butadiene-isoprene coordination polymerization was initiated by a binary molybdenum (Mo)-based catalytic system consisting of modified MoO2Cl2 as the primary catalyst, triethyl aluminum substituted by m-cresol as the co-catalyst and tris(nonyl phenyl) phosphate (TNPP) as the ligand. The effects of the amount of catalyst and type of co-catalyst were investigated in detail. Experimental results indicated that when the butadiene-isoprene coordination polymerization was initiated by the binary Mo-based catalytic system, the monomer conversion could reach 90%. The resulting butadiene units were primarily based on 1,2-structures, and the reactivity ratios of butadiene and isoprene were 1.13 and 0.31, respectively. The reaction in the catalytic system was attributed to the non-ideal and non-constant ratio copolymerization. When the addition of isoprene monomers was relatively low, the isoprene units on the butadiene-isoprene copolymers were primarily based on the 1,2- and 3,4-structures. Moreover, the orientation of active centers to 1,2- and 3,4-structures gradually decreased with an increase in the addition of isoprene monomers, which resulted in the generation of high vinyl butadiene-isoprene copolymers.
Highlights
Nowadays and into the future, low-cost, environmentally friendly and high-efficient materials are an enormous challenge in the material field
Experimental results showed that the butadiene-isoprene copolymerization could achieve high 1,2- and 3,4-stereoselective butadiene-isoprene copolymers using a binary molybdenum (Mo)-based catalytic system, composed of the aging-modified MoO2 Cl2 as the main catalyst, the m-cresol as a co-catalyst and tris(nonylphenyl)phosphite (TNPP) as a ligand
The tris(nonyl phenyl) phosphate (TNPP)-modified MoO2 Cl2 was prepared according to the following procedure: MoO2 Cl2 and ligand TNPP were first mixed at a certain proportion and had n-hexane added to dilute to the desired concentration
Summary
Nowadays and into the future, low-cost, environmentally friendly and high-efficient materials are an enormous challenge in the material field. PI possesses superb aging resistance, high wet skid resistance, low heat build-up, and can be applied as the rubber material for high-performance tire tread, accounting for why there exists more 1,2- and 3,4-structures, thereby resulting in the decrease in main-chain double bonds and in the increase of vinyl group content [9,10,11,12]. Y. Hu et al [5] and Tanaka et al [29] fabricated butadiene-isoprene copolymers with a high molecular weight distribution, low molecular weight and high cis-1,4 structure content by employing an Nd-based catalytic system to initiate the copolymerization. Experimental results showed that the butadiene-isoprene copolymerization could achieve high 1,2- and 3,4-stereoselective butadiene-isoprene copolymers using a binary molybdenum (Mo)-based catalytic system, composed of the aging-modified MoO2 Cl2 as the main catalyst, the m-cresol as a co-catalyst and tris(nonylphenyl)phosphite (TNPP) as a ligand. The effects of dosage of various components in catalytic system on the butadiene-isoprene copolymerization were explored as well
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